1. Field of the Invention
The present invention relates to an emulsion for pressure-sensitive adhesive which exhibits high adhesive strength to hard-to-adhere adherend such as polyolefin, high resistance to water, and high cohesive strength.
2. Description of the Related Art
In consideration of various factors such as environmental protection, safety in the working environment, resource saving, cost etc. there has been a large trend in recent years away from supplying solvent based adhesives (using an organic solvent as solvent medium) and more to supplying non-solvent adhesives (which do not use organic solvents). Amongst these non-solvent adhesives, pressure-sensitive adhesives emulsion have been favored in consideration of their general-purpose properties and workability. However, with these emulsion for pressure-sensitive adhesives, it is necessary to have a dispersant such as emulsifier in order to disperse the non-soluble pressure-sensitive adhesive polymer into the aqueous medium. Such a dispersant is water-soluble material, and there has been a problem that the resultant pressure-sensitive adhesive coating exhibits poor water-resistance.
The International Publication WO96/29373, filed by the present inventors, discloses an emulsion for pressure-sensitive adhesive which exhibits high water resistance. In the preparation of the emulsion, a compound which can chemically bond to the dispersant is added to the emulsion. After the emulsion is formed into a film, the carboxyl groups in the dispersant react with the compound, thereby nullifying the hydrophilic nature of the dispersant. The pressure-sensitive adhesive products produced using the emulsion has high water resistance.
It is true that the emulsion for the pressure-sensitive adhesive disclosed in the International Publication WO96/29373 can give high water resistance to the pressure-sensitive adhesive products. However, in recent years, there is an increasing demand for the pressure-sensitive adhesive products with superior adhesive properties including high adhesive strength, adhesion to polyolefin, and cohesive strength at high temperature, on top of high water resistance. In order to meet the demand, further studies have been conducted. As a method for providing such a pressure-sensitive adhesive products, it has been suggested to change the composition of the monomers for the pressure-sensitive adhesive polymer which is a component of the emulsion. As another method, it has been suggested that an adhesive strength modifier such as tackifier is added to the pressure-sensitive adhesive emulsion. However, most of tackifier are oil-soluble compound. When they are added to the pressure-sensitive adhesive emulsion, they require a large amount of emulsifier to be dispersed in water. The use of a large amount of emulsifier causes the deterioration in the water resistance of the pressure-sensitive adhesive products.
It is an object of the aspect of the present invention to provide an emulsion for pressure-sensitive adhesive which is capable of producing pressure-sensitive adhesive products having high resistance to water, and excellent adhesive properties such as high adhesive strength, adhesion to polyolefin, and high cohesive strength at high temperature.
In an aspect of the present invention, an emulsion for pressure-sensitive adhesive includes as essential components: a pressure-sensitive adhesive polymer (A) having a glass-transition temperature of xe2x88x9280 to xe2x88x9220xc2x0 C., a weight-average molecular weight of 150,000 or larger, and a carboxylic acid value of 30 or smaller; a rosin derivative (B) having a weight-average molecular weight of 100,000 or smaller, and containing at least part of the carboxyl groups being alkali salt with a carboxylic acid value of 190 or larger before alkalization; and a compound (C) having a weight-average molecular weight of 100,000 or smaller, and having no carboxyl group but having at least one functional group reactive with a carboxyl group in its molecule. The amount of the rosin derivative (B) is 2 to 30 mass percent when the total amount of the pressure-sensitive adhesive polymer (A) and the rosin derivative (B) in the emulsion is defined as 100 mass percent, and the compound (C) is contained in the emulsion so that the functional group of the compound (C) is in an amount of 0.05 to 10 equivalent with respect to one equivalent of the carboxyl groups of the rosin derivative (B) before alkalization.
The emulsion for pressure-sensitive adhesive of the present invention contains, as essential components, a pressure-sensitive adhesive polymer (A), a rosin derivative (B) and a compound (C). The most outstanding feature of the present invention resides in that the rosin derivative (B) having carboxyl groups is stabilized in the form of alkali salt in the emulsion without no need of much help of an emulsifier, and after the emulsion forms a pressure-sensitive adhesive layer, the carboxyl groups in the rosin derivative (B) (substantially, the carboxyl groups in the rosin derivative (Bxe2x80x2), as will be described later) are chemically reacted with the compound (C) to nullify the hydrophilic nature of the rosin derivative (B). The rosin derivative (B) can sufficiently show its ability of improving adhesive strength while the layer keeps its water resistance high. Hereinafter, the present invention will be described in detail. In the description, the term xe2x80x9cpolymerxe2x80x9d includes not only homopolymer but also multi-polymer including copolymers and terpolymers. It should be appreciated that the pressure-sensitive adhesive polymer (A), the rosin derivative (B) and the compound (C) are compounds different to one another.
First, the pressure-sensitive adhesive polymer (A) which is the first essential component will be described. The pressure-sensitive adhesive polymer (A) is a polymer which can display pressure-sensitive adhesiveness in the range of temperatures at which pressure-sensitive adhesive products are generally used. There are two types of polymer as the pressure-sensitive adhesive polymer (A): one type does not dissolve in water and alkali aqueous solution but can be emulsified by water-soluble emulsifier other than the polymer (A) and be made into a water dispersion and the other type can emulsify in itself. The latter type is obtained by using an emulsifier having reactivity with a monomer for the polymer (A). By use of the reactive emulsifier such as emulsifier having an ethylenically unsaturated double bond in the emulsion polymerization, the reactive emulsifier chemically bonds to the molecular chains of the pressure-sensitive adhesive polymer by polymerization. As a result, the polymer incorporated with the reactive emulsifier is obtained, and the polymer can emulsify in itself. In this invention the latter type is preferably used as well as the former type as the pressure-sensitive adhesive polymer (A).
A glass-transition temperature (Tg) of the pressure-sensitive adhesive polymer (A) is in the range of xe2x88x9280 to xe2x88x9220xc2x0 C. The pressure-sensitive adhesive polymer (A) having the Tg of xe2x88x9220xc2x0 C or higher may not exhibit its pressure-sensitive adhesiveness at a room temperature in some cases. To avoid this trouble, the upper limit of the Tg is determined to xe2x88x9220xc2x0 C. Contrary to this, the Tg of lower than xe2x88x9280xc2x0 C. is not preferable because the cohesive strength at high temperature tends to deteriorate. The glass-transition temperature Tg (K) can be easily obtained b the calculation from the following Formula using the Tg (K) of each homopolymer described in xe2x80x9cPOLYMER HANDBOOK, the third edition (issued by John Wiley and Sons, Inc.)xe2x80x9d, or can be obtained using a differential scanning calorimetry apparatus (DSC) or a differential thermal analysis apparatus (DTA).       W    Tg    =                    W        1                    Tg        1              +                  W        2                    Tg        2              +    …    +                  W        n                    Tg        n            
wherein Wn is a mass fraction of each monomer; and
Tgn is the Tg (K) of the homopolymer of each monomer.
The pressure-sensitive adhesive polymer (A) has a weight-average molecular weight (Mw) of 150,000 or larger. If the Mw is smaller than 150,000, the adhesive properties become poor. The molecular weight is a value converted to polystyrene measured by a gel permeation chromatography (GPC) Similarly, the Mw and the Mn are values converted to polystyrene measured by a gel permeation chromatography (GPC). A polymer having a large molecular weight, specifically, the Mw of about 1,500,000 or more, does not dissolve in a solvent (tetrahydrofuran; THF) which is used in the measurement using a GPC. Therefore, the measurement of the molecular weight using a GPC becomes impossible, and an accurate Mw cannot be obtained. In this case, however, it means that the polymer which does not dissolve in THF has a molecular weight of about 1,500,000 or more. Such a polymer is preferably used in the present invention. The solubility of the polymer is evaluated by the following steps:
(1) The pressure-sensitive adhesive polymer is properly sampled, and the mass of the sample in a dry state is measured (if the sample is an emulsion, the weight of the sample is measured after the water is evaporated therefrom.);
(2) The dried sample is put into tetrahydrofuran 10 times as heavy as the sample in mass, and the mixture is left at a temperature in the range from a room temperature to 40xc2x0 C. for 24 hours while stirred sometime. The dissolution of the sample may be promoted by the application of heat or supersonic waves;
(3) After 24 hours, the mixture is filtered through a wire gauze having 300 meshes, and the sample remaining on the wire gauze is dried and its mass is measured. The remaining sample on the wire gauze is regarded as an insoluble portion of the sample, and its weight is expressed by an initial mass percentage; and
(4) If the insoluble portion is 50 mass percent or more, it is judged that the sample is insoluble in tetrahydrofuran, and has a Mw of 1,500,000 or larger. In this case, the measurement of the molecular weight of the sample is regarded to be impossible. If the insoluble portion is less than 50 mass percent, the molecular weight of the sample dissolved in the solution of tetrahydrofuran is measured by a gel permeation chromatography.
The pressure-sensitive adhesive polymer (A) has an acid value (i.e. carboxyl group value) of 30 or smaller. The acid value of larger than 30 is not preferable, because the Tg tends to be higher than xe2x88x9220xc2x0 C. In addition, in this case, the compound (C) reacts with the carboxyl groups in the pressure-sensitive adhesive polymer (A), and the polymer chains in the pressure-sensitive adhesive polymer (A) are crosslinked. This results in lowering the adhesive strength of the pressure-sensitive adhesive product. In the present invention, the acid value, i.e. the carboxylic acid value, is obtained by dissolving 1 g of compound having carboxyl groups into a good solvent, and then subjecting the mixture to a neutralization titration with KOH. The amount of the KOH needed in the neutralization titration is expressed by a unit of mg, and this value is adopted as the acid value.
Specific examples of the pressure-sensitive adhesive polymer (A) include rubber based polymers such as natural rubbers, styrene-isoprene-styrene (SIS) block copolymers, styrene-butadiene-styrene (SBS) block copolymers, and synthetic rubbers, and polymers is obtained by polymerization of monomers having ethylenically unsaturated double bond. Among them, acrylic polymers is obtained by polymerization of monomers including alkyl (meth) acrylate as a main component are preferable because they give high adhesive properties to the resultant pressure-sensitive adhesive product.
As the alkyl(meth)acrylate which constitutes the acrylic polymers, one or more kind of alkyl (meth)acrylate monomer having an alkyl group having 4 to 12 carbon atoms is preferable, and the specific examples thereof include butyl (meth)acrylate, amyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, and dodecyl (meth)acrylate.
The acrylic polymer may be composed of the alkyl (meth)acrylates alone, or may be composed of the alkyl (meth)acrylate and the other monomers which are copolymerized with each other. In the latter case, in order to give high adhesive properties to the resultant pressure-sensitive adhesive product, it is preferable that 60 mass percent or more of alkyl (meth)acrylate is used with respect to the entire monomers.
Specific examples of the other monomers include (meth)acrylic acid, cycloalkyl (meth)acrylate, (meth)acrylates having alkyl groups with 3 or less carbon atoms, (meth)acrylates having carboxyl groups, (meth)acrylates having hydroxyl groups such as 2-hydroxyethyl (meth)acrylate, aromatic unsaturated hydrocarbons such as styrene and xcex1-methyl styrene, vinyl esters, vinyl ethers such as methyl vinyl ether, unsaturated cyano compounds such as acrylonitrile, and nitrogen-containing monomers such as N-isopropylacrylamide, N-vinylpyrrolidone, and N, N-dimethylaminoethyl (meth)acrylate.
Next, the rosin derivative (B) which is the second essential component in the pressure-sensitive adhesive emulsion of the present invention will be described. The rosin derivative (B) has weight-average molecular weight of 100,000 or smaller, and having carboxyl groups so that its acid value becomes 190 or larger before alkalization. A part or all of the carboxyl groups thereof is alkali salt. For convenience, the rosin derivative having carboxyl groups before alkalization (being made into alkali salt) is referred to as a rosin derivative (Bxe2x80x2).
In the present invention, the xe2x80x9crosin derivativexe2x80x9d is a rosin which has been subjected to at least carboxylic acid modification, as distinct from rosins derived from pine which are roughly classified into gum rosins, wood rosins, and tall oil rosins. Rosins originally have carboxyl groups, and the acid value of most of them never exceeds 190 as far as they are not subjected to carboxylic acid modification. The carboxylic acid modification is conducted by reacting the rosins with a carboxylic acid such as acrylic acid, itaconic acid, fumaric acid, and maleic acid to introduce the carboxyl groups into the rosins. On top of the above-described rosin, rosins such as hydrogenated rosin, disproportionated rosin, and polymerized rosin may be used as far as they have an acid value of 190 or larger. Among them, hydrogenated rosin is effective in giving high weatherability and high yellowing resistance to the resultant pressure-sensitive adhesive product.
The rosin derivative is a tackifier, as is well-known to one skilled in the art. The rosins have an effect of improving an adhesive strength. Therefore, when the pressure-sensitive adhesive emulsion containing the rosin derivative (B) is coated, the rosin derivative (Bxe2x80x2) enhances the adhesive strength of the coating. If the emulsion does not contain the rosin derivative (B) and such an emulsion is applied onto the surface which has been subjected to a releasing treatment with a silicone resin and therefore has a low surface energy, the emulsion is repelled on the surface (that is, the emulsion does not form a layer but forms a plurality of droplets.) and cannot be successfully spread onto the surface . Contrary to this, if the emulsion contains the rosin derivative (B), there is no such a problem. This is because a part of the rosin derivative (B) is dissolved in the aqueous phase of the alkaline emulsion in the state that its carboxyl groups are made into alkali salt, and that the rosin derivative (B) decreases dynamic surface tension of the emulsion.
In the pressure-sensitive adhesive emulsion, it is conceived that the rosin derivative (B) is in the state described below. A part of the rosin derivative (B) is dissolved in the aqueous phase of the alkaline emulsion in the state that its carboxyl groups are made into alkali salt. The another part thereof is in the form of oil-drop in the emulsion, and is stabilized by its carboxyl groups or the alkali salt thereof. Also a part of the rosin derivative (B) of which carboxyl groups are alkali salt is adsorbed onto the surface of the oil-drop of the pressure-sensitive adhesive polymer (A), thereby serving as an emulsifier for stabilizing the oil-drops of the pressure-sensitive adhesive polymer (A). In combination of these features, the rosin derivative (B) can be stably present in the pressure-sensitive adhesive emulsion of the present invention. The alkaline means the condition of pH 7 or more.
In order to be stable in the pressure-sensitive adhesive emulsion, the rosin derivative (B) having carboxyl groups before alkalization, i.e. the rosin derivative (Bxe2x80x2), is required to have an acid value of 190 or larger. If the rosin derivative (Bxe2x80x2) has an acid value of less than 190, the rosin derivative (B) cannot be stably present in the emulsion even if all the carboxyl groups of the rosin derivative (Bxe2x80x2) are made into alkali salt. The reason of this is as follows. When the rosin derivative (Bxe2x80x2) having an acid value of less than 190 is used, a large amount of other kind of emulsifier is required in order to disperse the rosin derivative (B) into the emulsion in a stable state. Without the large amount of emulsifier, the rosin derivative (B) is not sufficiently emulsified, and the oil-drops of the rosin derivative (B) bond to each other in the emulsion. As a result, the rosin derivative (B) coagulate and settle in the emulsion. In addition, the use of the large amount of the emulsifier results in poor water resistance of the film made of the pressure-sensitive adhesive emulsion.
The preferable acid value of the rosin derivative (Bxe2x80x2) is 210 or larger. Setting the acid value as above improves stability of the rosin derivative (B) in the emulsion. If the acid value is set exceeding larger than the above, water resistance of the resultant pressure-sensitive adhesive product is deteriorated despite the effect of nullifying hydrophilic nature by compound (C) which will be described later. In view thereof, the acid value of the rosin derivative (Bxe2x80x2) is 270 or smaller preferably.
By employing the following steps, the rosin derivative (B) can be easily present in the emulsion in a stable state. First, an emulsion of the pressure-sensitive adhesive polymer (A) is synthesized by emulsion polymerization using an emulsifier, and then an alkaline aqueous solution such as ammonia water is added thereto to make the emulsion alkaline. After that, the rosin derivative (Bxe2x80x2) having an acid value of 190 or larger is added to the emulsion. A part or all of the carboxyl groups of the rosin derivative (Bxe2x80x2) added to the emulsion becomes alkali salt, and as a result, the rosin derivative (Bxe2x80x2) becomes the rosin derivative (B).
As described above, the rosin derivative (B) is stably present in the emulsion without much help of an emulsifier. By using the rosin derivative (B), the absolute amount of the emulsifier in the emulsion is decreased. When the emulsion is formed into a film, alkali is evaporated therefrom, and the rosin derivative (B) becomes the rosin derivative (Bxe2x80x2) again. In the resultant film, a large amount of carboxyl groups derived from the rosin derivative (Bxe2x80x2) is present. In the present invention, the rosin derivative (Bxe2x80x2) is reacted with the compound (C) so that the carboxyl groups of the rosin derivative (B) chemically react with the functional groups having reactivity with carboxyl groups of the compound (C). Through this reaction, the carboxyl groups are consumed, and their hydrophilic nature is nullified. As a result, the film has high water resistance.
The molecular weight of the rosin derivative (B) (substantially, the molecular weight of the rosin derivative (Bxe2x80x2)), expressed by a weight-average molecular weight (Mw) is 100,000 or lower. If the Mw is larger than 100,000, the resultant film may have low transparency when the compatibility between the rosin derivative (B) and the pressure-sensitive adhesive polymer (A) is not good. The upper limit of Mw may be preferable 10,000, more preferable 6000, further more preferable 3000. The preferable lower limit of the Mw is 100. If the Mw is smaller than 100, the rosin derivative (B) does not have a sufficient effect of improving an adhesive strength.
The rosin derivative (Bxe2x80x2) preferably has a softening point of 200xc2x0 C. or lower. More preferably, the softening point is in the range of 80 to 180xc2x0 C. If the softening point is lower than 80xc2x0 C. is used, the cohesive strength of the pressure-sensitive adhesive product tends to deteriorate. However, the rosin derivative (Bxe2x80x2) having a softening point of lower than 80xc2x0 C may be exceptionally used in the case where the pressure-sensitive adhesive product is intended for use in an environment at a low temperature, or the pressure-sensitive adhesive product is required to have high adhesiveness to an adherend having a rough surface.
In the emulsion, the amount of the rosin derivative (B) is 2 to 30 mass percent (solid content) when the total weight of the pressure-sensitive adhesive polymer (A) is defined as 100 mass percent. The rosin derivative (B) of less than 2 mass percent has a poor effect of improving the adhesive properties. Contrary to this, the rosin derivative (B) of larger than 30 mass percent destroys the balance of the adhesive properties. More preferably, the amount of the rosin derivative (B) is 10 to 23 mass percent.
Lastly the compound (C), which is the third essential component of the emulsion for pressure-sensitive adhesive will be described. The compound (C) has no carboxyl group, but has at least one functional group which has a reactivity with a carboxyl group in its molecule. After the pressure-sensitive adhesive emulsion is formed into a film, the compound (C) is reacted with the rosin derivative (Bxe2x80x2) so that the carboxyl groups of the rosin derivative (Bxe2x80x2) are reacted with the functional group of the compound (C), resulting in nullifying the hydrophilic nature of the rosin derivative (Bxe2x80x2). As a result, the water resistance of the film is improved.
For this reason, the compound (C) is required to have at least one functional group reactive with the carboxyl groups of the rosin group (Bxe2x80x2). Examples of the functional group include glycidyl group, aziridinyl group, oxazolinyl group, and isocyanate group. When the compound (C) has an isocyanate group, it is preferable to use the compound (C) with the isocyanate group blocked (blocked isocyanate), because the isocyanate group reacts with water which is a medium of the emulsion. As described above, no carboxyl group is contained in the compound (C). If the compound (C) has a carboxyl group, the functional group of another compound (C) reacts with the carboxyl group of the former compound (C). Therefore the functional group of the later compound (C) is consumed. As a result, the compound (C) loses the reactivity with the carboxyl groups of the rosin derivative (Bxe2x80x2), although it is a property required for the compound (C).
As described above, the compound (C) is necessary at the chemical reaction between the rosin derivative (Bxe2x80x2) and the compound (C) after coating of the emulsion. Therefore the compound (C) should exist in the emulsion before coating. The compound (C) may be dissolved in water or oil, specifically the compound (C) may exist in water phase in the emulsion or in the oil-drop of the pressure-sensitive adhesive polymer (A). The preferable Mw of the compound (C) is smaller than 100,000. If the Mw is larger than 100,000, in the both cases of the compound (C) being water-soluble and oil-soluble, the compound (C) can not dissolve easily in water or oil. In view of the solubility to the emulsion, the upper limit of Mw of the compound (C) may be preferable 10,000, more preferable 5000.
Specific examples of the compound (C) is as follows:
glycidyl group-containing compounds: aliphatic oxides such as propylene oxide; aromatic oxides such as styrene oxide; alicyclic epoxides such as cyclohexene oxide; aliphatic glycidyl ethers such as butyl glycidyl ether and EPOLIGHT(copyright) M-1230 (a product of Kyoeisha Chemical Co., Ltd.); armoatic glycidyl ethers such as phenyl glycidyl ether; glycidyl esters such as glycidyl (meth)acrylate; glycidyl amine compounds such as TETRAD(copyright) series (products of Mitsubishi Gas Chemical Co., Ltd.); and polyglycidyl ethers such as DENACOL(copyright) series (products of Nagase and Co., Ltd.),
aziridinyl group-containing compounds: aliphatic aziridines such as butylaziridine; aromatic aziridines such as phenylaziridine; unsaturated group-containing aziridines such as 2-(1-aziridinyl) ethyl(meth)acrylate; and CHEMITITE(copyright) series (products of Nippon Shokubai Co., Ltd.),
oxazolinyl group-containing compounds: aliphatic oxiazolines such as 2-methyl oxazoline; aromatic oxazolines such as 2-phenyl oxazoline; unsaturated group-containing oxazolines such as 2-isopropenyl-2-oxazoline; and EPOCROSS(copyright) series (products of Nippon Shokubai Co., Ltd.),
isocyanate group-containing compounds: general-purpose isocyanates such as tolylene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI); blocked polyisocyanates such as DESMODULE AP STABLE and DESMODULE CT STABLE (products of Sumitomo Bayer Co., Ltd.); blocked isocyanate-containing prepolymers such as DESMOCUP 11 (a product of Daiichi Kogyo Seiyaku Co., Ltd.); and water dispersion type blocked isocyanates such as ELASTRON series and ELASTRON BN series (products of Daiichi Kogyo Seiyaku Co., Ltd.).
Among them, glycidyl amine compounds (TETRAD(copyright)-C and TETRAD(copyright)-X, products of Mitsubishi Gas Chemical Co., Ltd.) and aziridinyl group-containing compounds (CHEMITITE(copyright) PZ-33 and CHEMITITE(copyright) DZ-22, products of Nippon Shokubai Co., Ltd.) have high reactivity, and are preferably used.
The amount of the functional group having reactivity with a carboxyl group of the compound (C) is in the range of 0.05 to 10 equivalent with respect to one equivalent of the carboxyl group of the rosin derivative (B) (in this case, the carboxyl group means both the carboxyl group itself and that in the form of alkali salt. Substantially, the carboxyl group of the rosin derivative (Bxe2x80x2)). The compound (C) in an amount of less than 0.05 equivalent has no sufficient effect of improving the water resistance. The above amount may be preferable in the range of 0.1 to 5 equivalent.
The emulsion of this invention may contain the water-soluble emulsifier. The emulsifier is necessary to disperse the oil-soluble pressure-sensitive adhesive polymer (A) in water stably, and keep the emulsion state. An emulsifier, i.e. a surface ative agent, has a hydrophilic group such as sulfonate group and carboxylate group, and a hydrophobic group such as hydrocarbon group, and has an ability of emulsifying. In the present invention, the emulsifier having no functional groups having reactivity with a carboxyl group is used. Since the compound (C) having such a functional group exists in the emulsion, the emulsifier is not necessary to have such a functional group. In view thereof, the emulsifier is a compound different from the compound (C).
The preferable Mw of the emulsifier is smaller than 100,000. The smaller Mw is the effect of decreasing the surface tension of the emulsion. This facilities the coating step of the emulsion. In view thereof, the upper limit of Mw of the emulsifier may be preferable 10,000, more preferable 3,000. In view of water resistance, the preferable acid value of the dispersant is 185 or smaller.
There are no particular limitation regarding the kind of the emulsifier. Specific examples of emulsifiers which can be used as emulsifier, anionic emulsifier such as sodium alkyl sulfates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyldiphenylether disulfonate, polyoxyethylene alkyl sulfates, polyoxyethylene alkylaryl sulfonate, naphthalene sulfuric acid formaldehyde condensates; nonionic emulsifier such as polyoxyethylene alkylethers, polyoxyethylene alkylaryl ethers, polyoxyethylene derivatives, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, grycerol fatty acid esters, polyoxyethylene fatty acid esters, alkylalkanol amides.
As the emulsifier, an emulsifier having a carboxyl group may be used. Specifically, the emulsifier is a carboxyl group-containing emulsifier such as basic acids having 8 to 28 carbon atoms. Examples thereof include: fatty acid soap; N-acylamino acids (salts); alkyl ether carboxylic acid such as MX-RLM series (products of Kao Corporation); acyl peptides; carboxyl betaine emulsifiers; amino carboxylic acids; polycarboxylic acid type polymer emulsifiers such as LATEMUL series, DEMOL series, POIZ series, and HOMOGENOL series (products of Kao Corporation); RA-1020, RA-1120, and RA-1820 (products of Nippon Surfactant Co., Ltd.); SLB-12, ULB-20, SL-20, SB-20, ST-2P, and IPU-22 (products of Okamura Seiyu Co., Ltd.); and PDSA-DB, PDSA-DA, DSA, and SUN HIBITTER-150 (products of Sanyo Kasei Kogyo Co., Ltd.). After the pressure-sensitive adhesive emulsion is formed into a film, the emulsifier is reacted with the compound (C) so that the carboxyl groups in the emulsifier react with the functional group of the compound (C). Through this reaction, the carboxyl groups are consumed, thereby giving high water resistance to the resultant pressure-sensitive adhesive product.
As the emulsifier for use in the emulsion polymerization, a carboxyl group-containing oligomer emulsifier which is capable of achieving excellent emulsion stability in the emulsion polymerization may be used. Specific example thereof is a dispersant disclosed in the International Publication WO96/29373. The dispersant is produced by polymerizing monomers containing an unsaturated carboxylic acid (for example, acrylic acid) as an essential component in the presence of alkyl mercaptan having 6 to 18 carbon atoms.
The aforementioned emulsifiers have no reactivity with a monomer for the pressure-sensitive adhesive polymer (A), and accordingly differ from the following reactive emulsifier. Therefore, in the emulsion, these non-reactive emulsifiers absorb the oil-drop of the polymer (A), but do not bond to the polymer chemically.
It is preferable to use a reactive emulsifier as the emulsifier. As an example of the reactive emulsifier used in this invention, there is a reactive emulsifier having an ethylenically unsaturated double bond and having reactivity with a monomer for the pressure-sensitive adhesive polymer (A). By use of the reactive emulsifier having double bond in the emulsion polymerization, the reactive emulsifier bonds to the molecular chains of the pressure-sensitive adhesive polymer (A) by polymerization, and no molecules of the reactive emulsifier exist alone. As a result, the emulsifier never causes the deterioration of the water resistance of the pressure-sensitive adhesive product.
Examples of the reactive emulsifier having the double bond is as follows. There may be used alone or in combination of two or more of them. 
containing anionic emulsifiers: such as sulfates of polyoxyethylene allylglycidyl nonylphenyl ether: as products available on the market known are ADEKARIA SOAP SE series (products of Asahi Denka Co., Ltd.), ELEMINOL JS series (products of Sanyo Kasei Co., Ltd.), LATEMUL S series (products of Kao Corporation), H3390A , H3390B (products of Daiichi Kogyo Seiyaku Co., Ltd.) and the like.
allyl group-containing nonionic emulsifiers: such as polyoxyethylene allylglycidyl nonylphenyl ether: as products available on the market known are ADEKARIA SOAP NE series (products of Asahi Denka Co., Ltd.) and the like.
allyl group-containing cationic emulsifiers: as products available on the market known are RF-751 (a product of Nippon Surfactant Co., Ltd.) and the like. 
group)-containing anionic emulsifiers: as products available on the market known are ELEMINOL RS series (products of Sanyo Kasei Co., Ltd.), ANTOX series (products of Nippon Surfactant Co., Ltd.) and the like.
(meth)acryloyl group-containing nonionic emulsifiers: as products available on the market known are RMA-560 series (products of Nippon Surfactant Co., Ltd.), and the like.
propenyl group (CH3xe2x80x94CHxe2x95x90CHxe2x80x94)-containing anionic emulsifiers: such as ammonium sulfate of polyoxyethylene nonyl propenyl phenyl ether: as products available on the market known are AQUARON HS series, AQUARON BC series (products of Daiichi Kogyo Seiyaku Co., Ltd.) and the like.
propenyl group-containing nonionic emulsifiers: such as polyoxyethylene nonyl propenyl phenyl ether: as products available on the market known are AQUARON RN series (products of Daiichi Kogyo Seiyaku Co., Ltd.) and the like.
The use amount of the emulsifier is 0.5 to 10 parts by mass with respect to 100 parts by mass of the monomers for the pressure-sensitive polymer (A). Aforementioned various kind of emulsifiers may be used in combination.
Hereinafter, preferable methods for producing the emulsion for pressure-sensitive adhesive of the present invention will be described. In a first method, the monomers for the pressure-sensitive adhesive polymer (A) is polymerized by emulsion polymerization using the emulsifier having no reactivity with a monomer for the pressure-sensitive adhesive polymer (A) and/or the reactive emulsifier having an ethylenically unsaturated double bond, and the condition of the resultant emulsion of the pressure-sensitive adhesive polymer (A) is turned into alkaline. Then, the rosin derivative (Bxe2x80x2) and the compound (C) are added to the emulsion. By employment of the polymerization of the pressure-sensitive adhesive polymer (A), the resultant emulsion can be used as an emulsion as it is. Therefore, the first method is a simple method for producing the emulsion for pressure-sensitive adhesive. The monomers for the pressure-sensitive adhesive polymer (A) may be polymerized by emulsion polymerization using the emulsifier and a known aqueous polymerization initiator under the known conditions.
The rosin derivative (Bxe2x80x2) can act as an emulsifier, because it has a large amount of carboxyl groups (which are hydrophilic groups) and also has an oil-soluble moiety (which is hydrophobic group) derived from the rosin. Taking advantage of this feature, it is possible to use the rosin derivative (Bxe2x80x2) as an emulsifier in combination with the emulsifier in the emulsion polymerization for preparing the pressure-sensitive adhesive polymer (A). In this case, the rosin derivative (Bxe2x80x2) in an amount corresponding to a part or all of the amount of the rosin derivative (B) to be present in the finally obtained pressure-sensitive adhesive emulsion is put into the polymerization vessel as an emulsifier at an initial stage of the emulsion polymerization. In the view of stability in the emulsion polymerization and storage of the emulsion, it may be preferably to use the emulsifier having no reactivity with a monomer for the pressure-sensitive adhesive polymer (A) and/or the reactive emulsifier having an ethylenically unsaturated double bond.
The condition of the emulsion may be turned into alkaline to change the rosin derivative (Bxe2x80x2) into the rosin derivative (B) at any stage of the emulsion polymerization. The pH of the water medium for use in the emulsion polymerization is adjusted to 7 or higher before, during, or after the emulsion polymerization so that the water medium has an alkaline condition. Into the alkaline water medium, the rosin derivative (Bxe2x80x2) is added. As a result, the emulsion containing the rosin derivative (B) can be obtained. The amount of the rosin derivative (Bxe2x80x2) corresponds to the amount of the rosin derivative (B) required to be present in the finally-obtained emulsion, and all the rosin derivative (Bxe2x80x2) may be added at once, or may be gradually added. If the rosin derivative (Bxe2x80x2) is in a solid state at a room temperature, it may be powdered and is added to the water medium. Alternatively, the rosin derivative (Bxe2x80x2) may be dissolved in an alkaline aqueous solution beforehand to prepare the rosin derivative (B), and the solution of the rosin derivative (B) may be added to the emulsion or the polymerization vessel. The rosin derivative (Bxe2x80x2) is preferably added at a temperature in the range of 0 to 90xc2x0 C.
Examples of the alkali compounds for preparing the alkaline emulsion or alkaline aqueous solution of the rosin derivative (B) include alkali metal compounds such as sodium hydroxide, alkaline earth metal compounds, alkyl amines such as methylamine, and ammonia. Among them, alkyl amines and ammonia are preferable, because they have high volatility, and therefore, after the pressure-sensitive adhesive emulsion is formed into a film, they evaporate and never remain in the dried film. The resultant film has high water resistance.
The timing of adding the compound (C) to the emulsion is not specifically limited. It is preferable that the compound (C) is added after the emulsion polymerization is finished and before the emulsion for pressure-sensitive adhesive is applied to a substrate. In this manner, the compound (C) does not chemically reacts with the rosin derivative (B) during the emulsion polymerization and during storage of the emulsion for pressure-sensitive adhesive. The compound (C) may be added to the emulsion as it is, or may be added as a water dispersion prepared using an emulsifier.
In the second method for producing the emulsion for pressure-sensitive adhesive, the pressure-sensitive adhesive polymer (A) is prepared by a polymerization other than emulsion polymerization beforehand. To the pressure-sensitive adhesive polymer (A), water, and the emulsifier are added, and the mixture is mechanically stirred to prepare an emulsion. To the emulsion, the rosin derivative (Bxe2x80x2) and the compound (C) are added, and as a result, the pressure-sensitive adhesive emulsion is obtained. In the third method, the pressure-sensitive adhesive polymer (A) and the rosin derivative (Bxe2x80x2) are respectively melt by the application of heat to mix together, and the mixture is formed into emulsion according to the above manner. In these cases, during or after the preparation of the emulsion of the pressure-sensitive adhesive polymer (A), the condition thereof is adjusted to alkaline, and the rosin derivative (Bxe2x80x2) is added thereto. The compound (C) is preferable added to the emulsion that is obtained by emulsifying the pressure-sensitive adhesive polymer (A) and before the emulsion for pressure-sensitive adhesive is applied to a substrate. Instead of the emulsion polymerization, the pressure-sensitive adhesive polymer (A) can be produced by a solution polymerization or a bulk polymerization. It is also possible that the pressure-sensitive adhesive polymer (A) is produced by an emulsion polymerization or a suspension polymerization, and then is separated from water before used. It is possible to add conventionally known additives such as cross-linking agents, wetting agents, viscosity adjustors, thickners, defoaming agents, modifiers, tackifiers, pigments, coloring agents, fillers, anti-oxidants, UV absorbents, and UV stabilizers to the extent that they do not have a bad effect on the emulsion for pressure-sensitive adhesive or the pressure-sensitive adhesive product.
The emulsion for pressure-sensitive adhesive is used in producing pressure-sensitive adhesive products. For example, the emulsion for the pressure-sensitive adhesive is applied onto a substrate such as plastic film, paper, non-woven fabric, and foam, or a release sheet, and is dried to form a film. There are pressure-sensitive adhesive products in which a layer of the pressure-sensitive adhesive is formed only on its single side, and in which a layer of the pressure-sensitive adhesive is formed on its both sides. There are also pressure-sensitive adhesive products including a layer of the pressure-sensitive adhesive alone having no substrate. On top of the pressure-sensitive adhesive products, the emulsion of the present invention may be used in various other applications such as adhesives, paints, paper processing agents, fiber processing agents, mortar improving agents, and sealing agents.